IONIC EQUILIBRIUM

Solution to Subjective Problems

LEVEL – I

[salt ]
1. pH = pKa+ log
[acid]
Let x mole of HCl be added. x mole HCl will react with x mole NaCN to form x mole
HCN.
NaCN + HCl  NaCl + HCN
More correctly,
CN– + H+  HCN
0.01 x 0
0.01 – x 0 0
Thus,
0.01  x 
8.5 = – log (4.1  10–10) + log 
 x 
 0.01  x 
 log  = – 0.8872
 x 
0.01  x
 = 0.1296
x
 x = 8.85  10–3M

2. Let the solubility of Ca(OH)2 is pure water be S mole L–1

Ca(OH)2(s) Ca2+ + 2OH–
s 2s
2+ – 2
Ksp= [Ca ] [OH ]
4.42  10–5 = s(2s)2 = 4s3
4.42  10 5
s= 3 = 0.0223 mole L–1
4
0.0223
No. of mole of Ca2+ ion in 500 mL of saturated solution = = 0.01115
2
Upon addition of 500 mL of 0.4 M NaOH to 500 mL of saturated solution of Ca(OH)2,
the concentration of NaOH i.e. OH– ion will be halved. That is
0 .4
[OH–] = = 0.2 M
2
K sp 4.42  10 5
[Ca2+] =  = 0.001105 M
[OH  ]2 (0.2)2
Thus, no. of mole of Ca2+ or Ca(OH)2 ppted out
= 0.0115 – 0.001105 = 0.010045
Mass of Ca(OH)2 ppted = 0.010045 74
= 0.7433g = 743.3 mg

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RSM79Ph-IIIECH(H&S)2

3. We have already seen that even though when CH3COOH is titrated with NaOH the
reaction does not go to completion but instead reaches equilibrium. We can assume
that the reaction is complete and then salt gets hydrolysed because, this assumption
will help us to do the problem easily and it does not effect our answer.
K wK a
 [H+] =
C
First of all we would calculate the concentration of the salt, CH3COONa. For
reaching equivalence point,
N1V1 = N2V2
 0.1  25 = 0.05  V2  V2 = 50 ml
0.1 25 0.1
Therefore [CH3COONa] = 
75 3
10 14  1.8  10 5
[H+] = = 2.32  10–5
0.1 3
 pH = – log 2.32  10–5 = 8.63

4. pH = – log[H+]
4.18 = – log [H+]
[H+] = 6.61  10–5
H2CO3 H+ + HCO 3
[H ][HCO 3 ]
Ka =
[H2CO 3 ]
6.61 10 5  [HCO 3 ]
or, 4.45  10–7 =
.01

 [HCO 3 ] = 6.73  10–5

again, HCO 3 H+ + CO 3 
[H ][[CO 3  ] 6.61 10 5 [CO 3  ]
 Ka2 = = 4.69  10–11
=
[HCO 3  ] 6.73  10  5
 [CO 3  ] = 4.8  10–11

5. We have,
[acid] 0 .5
[H+] = Ka = 1.74  10–5  -= 5.8  10–5
[salt ] 0.15
KW 1 10 14
 [OH–} = + = 1.7  10–10
[H ] 5.8  10  5
Now, ionic product of Fe(OH)3 = [Fe3+]  [OH–]3 = 0.25  [1.7  10–10)3
 Q  Ksp, the precipitate will form

6. We know,
Ksp(PbS) = [Pb+2] [S–2]
Since lead salt is completely dissociated, [Pb+2] is equal to the concentration of lead
salt, i.e. [Pb+2] = 0.001M. If[S–2] is the concentration of S–2 required to just start
precipitation of PbS.

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 RSM79Ph-IIIECH(H&S)3

3.4  10 28
[S–2] = = 3.4  10–25
0.001
Now the addition of HCl with suppress the dissociation of H2S to that extent that [S–2]
= 34  10–25 (M)
 HCl is completely ionised,  [H+] = [HCl]
Let [HCl] be x. Therefore [H+] = x
H2S 2H+ + S–2
At equilibrium [H2S] = 0.1 – 3.4  10–25  0.1
" [H+] = 2  3.4  10–25 + x  x
[S ] = 3.4  10–25
–2

[H ]2 [S 2 ]
Ka =
[H2S]
x2 (3.4  10 25 )
1.1  10–23 =
3.4  10  25
 x = 1.80
This any concentration of HCl greater than 1.8 M
Will just prevent precipitation

7. pH before addition
The solution containing NH3 and NH3Cl is a base buffer mixture for which
[salt ] 0.1
pOH = pKb + log = – log(1.8  10–5) + log = 4.74 + 0
[base] 0.1
 pH = 14 – 4.74 = 9.26
pH after addition of
a) 0.02 moles of HCl(g)
0.02 moles of HCl will react with 0.02 moles of NH3 i.e. NH4OH to form 0.02
moles of NH4Cl (salt)
Thus,
[NH4OH] = 0.1 – 0.02 = 0.08 M
[NH4Cl] = 0.1 + 0.02 = 0.12 M
0.12
 pOH = 4.74 + log = 4.92
0.08
pH = 9.08
Thus, pH = 9.08 – 9.26 = – 0.18

b) 0.02 moles of NaOH

Upon addition of 0.02 mole sof NaOH, there will be interaction between NH4Cl
and NaOH
NH4Cl + NaOH NH4OH + NaCl
NH4+ + OH– NH4OH
0.1 M 0
(0.1 – 0.02)
= 0.08 M 0.02 M
Thus, [NH4OH] = 0.12 M
[NH4Cl] = 0.08 M

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RSM79Ph-IIIECH(H&S)4

0.08
pOH = 4.74 + log = 4.586
0.12
pH = 9.4314
pH = 0.1761 unit

8. Aqueous solution of NH4Cl will be acidic due to hydrolysis of the salt.

NH4+ + H2O NH4OH +H+
The pH of such a solution can be calculated using the formula
1
pH = [pKw – pKb – logC]
2
1
5 = [14 – (–log 1.8  10–5) – logC]
2
 10 = 14 – 4.74 – logC
 logC = 9.26 – 10 = – 0.74
 C = 1026  10–1 = 1.82  10–1 = 0.0182 M
1000 mL solution will have to contain 0.182 mole of NH4Cl
0.182
250 mL solution will have to contain mole of NH4Cl
4
0.182
=  53.5 g of NH4Cl
4
= 2.43 g of NH4Cl
(Molecular weight of NH4Cl = 53.5)
Thus, 2.43g of NH4Cl will have to be dissolved in 250 mL water so as to have a
solution of pH 5.

9. If Ka and Kb be the acid dissociation constant of HCN and base dissociation constant
of CN– i.e.
[H ][CN  ]
HCN H+ + CN–, Ka =
[HCN ]
[HCN ][OH  ]
CN– + H2O HCN + OH– Kb =
[CN  ]
Then Ka  Kb = [H+] [OH–] = Kw
K
 Ka = w
Kb
K Kw
Kh = w   Kb
Ka K w / Kb
We can also arrive at the same result if we consider the equilibrium
CN– + H2O HCN + OH–
This is hydrolysis equilibrium of CN– ion whose equilibrium constant is the hydrolysis
constant (Kh). The same equilibrium is also the base dissociation constant of CN–
ion.
So, Kh = Kb
pKb = 4.70  Kb = 10–4.70 = 100.30  10–5 = 2  10–5
So, Kh = 2  10–5

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 RSM79Ph-IIIECH(H&S)5

Kh 2  10 5
h=  = 6.3  10–3
C 0.5
% hydrolysis = 100 h = 6.3  10–1 = 0.63
[OH–] = Ch = 0.5  6.3  10–3 = 3.15  10–3 M
pOH = 2.5 and pH = 11.5

10. Pb(OH)2(s) Pb2+ + 2OH–

s 2s
Where s is the solubility of Pb(OH)2 in mole L–1 in water.
Ksp = s(2s)2 = 4s3 = 4 (6.7  10–6)3 = 1.2  10–15
pH of buffer = 8
 pOH = 6 and [OH–] = 10–6 M
Let the solubility of Pb(OH)2 in buffer solution of pH = 8, x mole L–1
Pb(OH)2(s) Pb2+ + 2OH–
x 10–6
x(10 ) = Ksp = 1.2  10
–6 2 –15

1.2  10 15
x= = 1.2  10–3M
10 12

LEVEL – II

1. Let the concentration of NH4Cl be x mole L–1, then concentration of NH3 in the
mixture be (0.6 – x) mole L–1. The mixture will be a basic buffer mixture for which
pOH is given by the formula.
[salt ]
pOH = pKb + log
[base]
x
5 = 4.7 + log ( pH = pOH = 14)
0.6  x
x
log = 0.3 = log2
0.6  x
x
 =2
0.6  x
 x = 0.4
Thus concentration of NH4Cl = 0.4 mole L–1
Concentration of NH3 = 0.2 mole L–1
g/L 4
Molarity of NaOH in solution = = = 0.1
MW 40
Added NaOH will react with NH4Cl in equimolecular proportion to give NH3 (i.e.
NH4OH).
NH4Cl + NaOH  NH4OH + NaCl
More appropriately
NH4+ + OH–  NH4OH
[NH4OH] = 0.2 + 0.1 = 0.3
[NH4Cl] = 0.4 – 0.1 = 0.3
0 .3
pOH = 4.7 + log = 4.7  pH = 9.3
0 .3

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RSM79Ph-IIIECH(H&S)6

Thus, pH of the buffer will increasing 0.3 unit i.e.

pH = 9.3 – 9 = 0.3

2. [H+] = Ka  C
10–3 = Ka  1
 Ka = 10–6
(conc. of weak acid solution being appreciable, we may neglect  in comparison to
unity.)
Total acid taken = 20  1 = 20 millimole

a) 10 mL 0.5 M NaOH i.e. 5 millimole of NaOH

HA + NaOH  NaA + H2O
5 millimole NaOH will react with 5 millimole HA (weak monobasic acid) to give 5
millimole salt (NaA) leaving behind 15 millimole acid unreacted.
Thus,
[salt ] 5 1
= 
[acid] 15 3
[salt ] 1
 pH = pKa + log = 6 + log = 6 – 0.417 = 5.523
[acid] 3

b) 20 mL 0.5 M NaOH i.e. 10 millimole NaOH

Salt formed = 10 millimole
Free acid = 10millimole
[salt ] 1
= =1
[acid] 1
pH = 6 + log1 = 6

c) 40 mL 0.5 M NaOH i.e. 20 millimole NaOH

Salt formed = 20 millimole
Free acid = nil
mil lim ole 20 1
[salt ]   
mL 60 3
The salt will get hydrolysed to produce OH– ion thereby rendering the solution
alkaline for which
1
pOH = [pKw – pKa – logC]
2
1 1
= [14 – 6 – log ]
2 3
1
= [14 – 6 + 0.477]= 4.23
2
 pH = 9.77

3. For determination of sulphide ion concentration, we have to consider the first as well
as second ionisation of H2S.
H2S H+ + HS–

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 RSM79Ph-IIIECH(H&S)7

[H ][HS  ]
K1 =
[H2S]
–
HS H+ + S2–

[H ][S2 ]
K2 = …(i)
[H2S]
Equation (i) corresponds to complete ionization of H2S.
H2S 2H+ + S2–
Given pH = 11
 [H+] = 10–pH = 10–11 M
[H2S] = 0.1 M
K1 = 5.7  10–8, K2 = 1.2  10–15-
Hence from equation (1), we get
[10 11]2 [S2  ]
5.7  10–8  1.2  10–15 =
0.1
2
[s ]
6.84  10–23 = 10–22 
0 .1
[S ] = 6.8  10 M
2- –2

4. Note that Ka of two acids is nearly same. In such cases, we have to consider H+ from
both HA & HB simultaneously. The concentration of HA & HB in the mixture = 0.5 M
[equal volumes are mixed ] = say ‘c’
HA  H+ + A–
HB  H+ + B–
Let x = [H+] from HA and Y = [H+] from HB
 [H+]final = x + y
( x  y )x ( x  y )y
KHA = & KHB =
c c
15 x
  6x = 5y
18 y
6 x 2  xy
substitute for y = x in KHA =
5 C
5x  6x
2 2
 1.5  10–5 =
2.5
x = 1.84  10 ; y = 2.21  10–3
–3

[H+] = x + y = 4.055  10–3

pH = – log10 (4.055  10–3)  pH = 2.392

5. The anion of the salt being conjugate base of a weak acid will hydrolyse in the
following three steps.
K 10 14
PO43– + H2O HPO42– + OH– K h1  w  = 10–2
K 3 1.0  10 12
Kw 10 14
HPO42– + H2O H2PO4–+ OH– Kh2   = 4  10–7
K2 2.5  10  8

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RSM79Ph-IIIECH(H&S)8

Kw 10 16
H2PO4– + H2O H3PO4 + OH–  K h3  3
= 2  10–12
K1 5.0  10
Kh3 and Kh3 being quite smaller as compared to K h1 it is wiseful to consider only the
1st step hydrolysis so as to simplify the calculation.
The pOH the solution may be given by the formula.
1
pOH = [pKw – pK3 – logC]
2
1 1
= [14 – 12 – log0.1] =  3 = 1.5
2 2
So, pH = 12.5

6. Let the number of millimole of weak base contained in 25 mL solution be x.

Upon addition of 10 mL 0.5 M HCl i.e. 5 millimole HCl, the salt formed will be 5
millimole and base remaining unreacted will be (x – 5) millimole.
For a base buffer mixture
base] [salt ]
[OH–] = K b [ i.e. pOH = pKb + log
[salt ] [base]
 pH = 8.6  pOH = 5.4 and [OH–] = 10–5.4
[ x  5]
So, 10–5.4 = K b …(1)
5
Upon addition of 25 mL 0.5 M HCl i.e 12.5 millimole HCl, the salt formed will be 12.5
millimole and base remaining unreactred will be (x – 12.5) millimole.
 pH = 8  pOH = 6 and [OH–] = 10–6
The mixture is again a basic buffer mixture for which
K ( x  12.5)
10–6 = b …(2)
12.5
Dividing equation (1) by (2)
2.5( x  5)
100.6 =
x  12.5
2.5( x  5)
4=
x  12.5
 4x – 50 = 2.5x – 12.5
 x = 25
No. of mil lim ole 25
Molarity of base solution = = =1
Volume in mL 25
Putting the value of x in equation (2): Kb= 10–6
Upon addition 0 mL acid
BOH B+ + OH–
C 0 0
C(1 – ) C C

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 RSM79Ph-IIIECH(H&S)9

Kb
[OH–] = C = C  K b  C (neglecting  in composition to unity which is true for
C
concentrated solution).
= 10 6  1 = 10–3M  pOH = 3 and pH = 11
At the end point:
The end point will reach when 50 mL 0.5 M HCl is added. 25 mL 1.0 M HCl i.e. 25
millimole of HCl will react with 50  0.5 i.e. 25 millimole of BOH to form 25 millimole
of salt. The total volume of solution will be 75 mL.
25 1
 [salt] =  M
75 3
The solution will be acidic due to salt hydrolysis. The pH of such a solution will be
given by the expression.
1
pH = [pKw – pKb – logC]
2
1 1
= [14 – 6 – log ] = 4.239
2 3

7. pH = 9.0  [H+] = 10–9 M and [OH–] = 10–5 M

[Mg2+] [OH–]2 = KSP
8.9  10 12
[Mg2+] = = 8.9  10–2 = 0.089 M
(10  5 )2
Thus in saturated solution of Mg(OH)2, only 0.089 mole l–1 of Mg2+ will remain
dissolved.
Hence the amount of Mg2+ to be precipitated out = 0.1 – 0.089
= 0.011 mol l–1

8. Molarity of ammonia may be calculated as,

x  d  10
M
mB
x = % solute by weight
d = density of solution
mB = molecular weight of solute.
10  0.99  10
= = 5.823
17
Kw = Ka  Kb
10–14 = 5  10–10  Kb
Kb = 2  10–5
We known, [OH–] = C  K b for monoacidic base.
= 5.823  2  10 5 = 0.01079 M
kw 10 14
[H+] =  = 9.268  10–12 M
[OH  ] 0.01079

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RSM79Ph-IIIECH(H&S)10

9. The solubility eqn. is

Cd(OH)2(s) Cd2+ + 2OH–
Ksp = [Cd2+] [OH–]2 = 2  10–14
Now (Cd2+] = 0.010 M (coming from CdCl2)
 Maximum [OH–] so that precipitation does not occur is
2.0  10 14
[OH–]2 = = 2  10–12
1.0  10  2
or [OH–] = 1.4  10–6 M
Now [OH–] is derived from
NH3 + H2O NH 4 + OH–
[NH 4 ][OH  ] [NH 4 ][1.4  10 6 ]
Kb =  1.8  10  5  or [NH 4 ]  1.3  10 1M
[NH 3 ] [0.010 ]
 NH4+ ion that must be supplied is 0.13 M[Assuming very small dissociation of
NH3/NH4OH in presence of NH4Cl]

10. C6H5NH2 + H2O C6H5 NH3 + –OH

Here C6H5NH2 is acting as a base to give conjugate acid C6H5 NH3

OH C H NH 


14
  = K w = 10
6 3 5
 Kb (C6H5NH2) =
C6H5NH 2  Ka 2.4  10  5

or
10 14

 
OH   1 10 8
.4  10  5 0.24
or [OH–] = 10–2 M
 Required conc. of NaOH = 10–2 M

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 RSM79Ph-IIIECH(H&S)11

Solution to Objective Problems

LEVEL – I

[In ]
1. pH = pKin + log , where pKin = 6
[HIn ]
[In  ] 1
For acid colour to predominates 
[HIn ] 10
 pH  6 – 1 i.e 5.0
[In  ]
for base colour to predominate 5
[HIn ]
 pH  6 + log5  pH  6.7
 (A)

2. “Complete dissociation” implies that interionic attraction has completely ceased to

exist. This condition in the case of a solution of strong electrolyte is achieved only at
infinite dilution when concentration of solution tends to zero.
 (C)

3. Solution of weak acid being concentrated, we can use the approximate

Ka 1
= i.e.  
C C
Thus, decreasing the conc. to one fourth,  will be doubled. Doubling of  means
doubling of percentage onization. Hence % onization will be 2x.
[H+] = Ka  C i.e. [H+]  C
If the conc. is decreased to one fourth of its original value H+ ion conc. will be halved.
Thus, after dilution [H+] = 0.5  10–3M
 pH = 3.3
 (D)

No. of moles of acid added per litre of buffer

4. Buffer capacity =
change in pH
0.006
= = 0.2
0.03
 (C)

5. [Ca2+] [SO42–] = 2.4  10–5

2.4  10 5
[Ca2+] = = 5  10–3M
4.8  10  3
1 L solution contains 5  10–3 mole of Ca2+ ions
1000 L solution will contain 5 mole i.e. 200 g Ca2+ ions
Taking density of aqueous solution to be unity
1000 kg i.e. 106 g solution contains 200g Ca2+ ions
Conc. of Ca2+ ion = 200 ppm
 (A)

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RSM79Ph-IIIECH(H&S)12

6. Water remains feebly ionised into H+ and OH– ions. H+ ion does not exist
independently but as H3O+ as shown below:
H2O + H2O H3O+ + OH–
 (D)

7. M(OH)2 will precipitate when

[M2+] [OH–]2  4.0  10–10
[OH–]  2.0  10–5 molar ( [M2+] = 1)
X(OH)3 will precipitate when
[X3+] [OH–]3  2.7  10–14
 [OH–]  3  10–5 molar ( [X3+] = 1)
Thus M(OH)2 requires less concentration of OH– ion for precipitation. Hence M(OH)2
will precipitate first.
 (B)

[salt ]
8. At the point of half neutralization the mixture will be an acid buffer with =1
[acid]
pH = pKa + log1
pKa = 5.7
Ka = 2.0  10–6
 (D)

9. [OH–] = 2  10–7
pOH = 14 – pH or – log [OH–]
(A)

10. AgCl Ag+ + Cl–

In CaCl2
CaCl2 Ca+2 + 2Cl–
0.01 0.01 20.01
In NaCl
NaCl Na+ + Cl–
0.01 0.01 0.01
In AgNO3
AgNO3 Ag+ + Cl–
0.05 0.05 0.05
common ion effect is maximum in AgNO3
So, S1 > S3 > S2 > S4
(B)

11. Since pH = 12 pOH = 14 – 12 = 2

[OH–] = 10–2M
We know Ba (OH)2 Ba++ + 2OH–
10 2
[Ba++] = M
2
 10 2 
KSP = [Ba++] [OH–]2 =    (10–2)2 = 5  10–7M3

 2 
(D)

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 RSM79Ph-IIIECH(H&S)13

12. Zn++ + 2H2O Zn(OH)2 + 2H+

 Kh =
ZnOH 2  H  2
Zn 

… (1)

Zn(OH)2 Zn++ + 2OH–

Kb =
Zn  OH 
  2
, Kw = [H+] [OH–]
ZnOH 2 
K 2w
 = Kh
Kb
 (B)

Kw 10 14
13. Ka =  = 1.8  10–16
[H2O] 55.5
(A)
14. C6H5COOH + NaOH C6H5COONa + H2O
After 0.5 0.5
neutralization
It is a buffer solution of weak acid and its salt
[salt ]
pH = pKa + log
[acid]
pKa = 4.2
Ka = 6.31  10–5
(A)

15. Old pH = 7
1
New [OH–] = 10–2  = 10–3
10
New pH = 11
Change is pH = 4
(A)

16. NH4+ being a conjugate acid of a weak base NH4OH will be a strong acid, and thus it
would get hydrolysed to give free H+ ion in solution.
NH4+ + H2O NH4OH + H+
Solution of all the other salts will be either alkaline or almost neutral.
(A)

17. If CO2 escapes from the system, the following equilibrium will not be attained
H2O + CO2 H2CO3 H+ + HCO3–
 [H+] will decrease
 (B)

18. A2X5 2A+5 + 5X–2

Ks = [A ] [X–2]5
+5 2

= (2x)2  (5x)5

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RSM79Ph-IIIECH(H&S)14

= 4x2  3125 x5 = 12500x7 = 1.25  104x7

 (D)

20. Kh for anilinium ion = 2.4  10–5M

K
Kh = w
Kb
10 14
Kb = = 4.1  10–10.
2.4  10  5

21. In NH3 medium acetic acid will be neutralized to form CH3COONH4 which being a
salt will remain completely ionized. On the other hand CH3COOH in aqueous
solution will be only partially dissociated. Thus, acetic acid will show more conduction
in NH3 than in water
 (D)

22. Equilibrium constant of the reaction

A– + H2O HA + OH– is really the hydrolysis constant of (Kh) of A– given as
K
Kh  w
Ka
 (A)

Kw
23. Ka = = 10–8
Kh
  K a V  2 = KaV
Which an equation of a straight line passing through the origin


2

Slope = tan = Ka


V

24. [H ]mixture = [0.5  10–3 + 0.5 + 10–4]<

+

pH = 3.26
 (B)

25. Ksp = 1.8  10–10

[Ag+] [Cl–] = 10–4  10–4= 10–8
 K spAgCl  [Ag+] [Cl–]
 (A)

26. pKw = 12.26

 Condition of neutrality pH = 6.13
Thus, pH = 6.2  6.13
Means alkaline
 (B)

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 RSM79Ph-IIIECH(H&S)15

27. HA H+ + A–
HB H++ B–
for HA
K a 1 = 2C
K a14  10 10
12 = 
C C
1 = 2  10 for C = 1 M
–5

Similarly  [H+] = C = 2  10–5  pH = 4.7

K a2
for HB, 22 =
C
1.8  10 5
= for C = 1M
C
2 = 4.2  10–3  [H+] = C = 4.2  10–3
pH = – log (4.2  10–3) = 2.37
(A)

28. At 15°C, Kw = 10–14. So at temperature below 25°C Kw  10–14

 pH  7 (for neutral solution or pure water)

No. of moles of base added / litre of buffer

29. Buffer capacity =
Change in pH
0.01 0.01
=  = 0.11
(6.832  6.745 ) 0.087
 (B)

30. Al3+ having high charge density will associate strongly with water through its
fractional negatively charged oxygen pole and in such interaction there will be
hydrolysis to some extent:
Al3+ + H2O [Al(OH)]2++ H+
The product cation may hydrolyse further
 (B)

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